Catalytic polymers from high boiling unsaturated products of petroleum pyrolysis



Oct. 23, 1945. w. c. AuLr 2,387,237

CATALYTIC PQLYMERS FROM HIGH VBOILING' UNSATURATED.

PRODUCTS OF PETROLEUH PYROLYSIS Filed Apr-11 1. 1941 2 sheets-sheet 1Oct 23, 1945. w. c. AULT 2,387,237

GATALYTIC POLYMERS FROM HIGH BOILING UNSATURATED PRODUCTS OF PETROLEUMPYROLYSIS Flled April 1. 1941 2 Sheets-Sheet 2 s Irgend/2) 12%; @iff o/0Nissa Grandma/d U0 OELLVWIQWVO Patented Oct. 23, 1945 CATALYVTICPOLYMERS FROM HIGH BOILING UNSATURATED PRODUCTS F PETROLEUM PYROLYSISWaldo C. Ault, Peoria, Ill., assigner to The United Gas ImprovementCompany, a corporation of Pennsylvania Application April 1, 1941, SerialNo. 386,232

11 Claims.

'I'he present invention relates to the catalytic polymerization of highboiling monomeric hydrocarbon material recovered from tar formeddurinvolving the pyrolytic decomposition. of petroleum oil with orwithout the aid of catalysts and to catalytic polymers of said monomerichydrocarbon material.

Various processes are known for the manufacture of combustible ga suchas carburetted water gas and oil gas, wher; ,n a petroleum oil such ascrude oil or a fraction thereof, for example, gas oil or residuum oil,is pyrolytically decomposed.

In such processes petroleum oil is pyrolyzed in vapor phase and atreduced partial pressures due to the presence of diluent gas such asblue water gas and/ or steam and at relatively high temperatures such as1300 F. average set temperature and above as measured by standard typeshielded thermocouples.

In such processes the gas leaving the gas-making apparatus is usually'rbrought into contact with water such as in the wash box, and as a resultthe tar which separates from the gas is usually recovered in the form ofan emulsion with water. Thus the tar emulsion in extreme cases maycontain as high as 95% water or even higher. In some cases the taremulsion may be in the form of a pasty solid of very high viscosity.Frequently, the tar emulsion will contain at least 50% water and in thisrespect differs from tars obtained in processes for the production ofcoal gas or coke oven gas, or in many oil cracking processes for theproduction of motor fuel, for in the latter processes the tar asrecovered is not in an emulsion form.

The recovered mixture of tar and water from gas-making operationsinvolving the decomposition of petroleum oil is usually iirst collectedin a settling tank for the separation of as much water as possible bylayer formation and decanta- 1 tion.

In accordance with conventional practice the relatively stable taremulsion which remains after separation of the water layer is usuallytreated ing the production of combustible gas by processes r accordingto some method of dehydration such as centrifuging or distillation.

Centrifugal methods of treating tar emulsions, however, separate onlythe tar and the water of the emulsion and do not separate lighter tarconstituents from the heavier. Furthermore, the presence of free carbonin the emulsion may give rise to operating difliculties.

The separation of the tar emulsion by distillation results in fractionswhich comprise (l) water, (2) a distillate from the tar comprisinglightoil and dead oil, and (3) residual tar.

For purposes of convenience in description, that portion of thedistillate boiling up to approximately 210 C. (410 F.) at atmosphericpressure will be designated light oil and that portion of the distillateboiling above approximately 210 C. (410 F.) at atmospheric pressure willbe designated dead oil. These may be separated by distillation.

The light oil fraction contains, among other things, valuable saturatedand unsaturated aromatic hydrocarbons such as benzene, toluene, xylene,styrene. methyl styrene, indene, etc.

The dead oil fraction contains naphthalene, methyl and other substitutednaphthalenes, and may contain anthracene, methyl anthracene, as well asnumerous other hydrocarbons for the most part as yet unidentiied.

The residual tar still contains polymerizable constituents.

The residual tar has a number of uses. For example, it may be used as aroad tar, or as a heavy liquid fuel. For both purposes the control ofthe viscosity of the residual tar is of importance because of its electupon the ease of handling.

Due to the fact that the tar is subjected to elevated temperatures forconsiderable lengths of time in ordinary distillation procedures of theprior art for breaking the emulsion and for the separation of light oiland dead oil as distillate, substantial polymerization is caused to takeplace. Such polymerization tends to reduce the quantity of distillate onthe one hand and t0 increase the 342,735 led June 27, 1940 by Edwin L.Hall and .Howard R. Batchelder, which has matured into Patent 2,366,899,granted January 9, 1945 Serial Number 353,034 led August 17, 1940 byHoward R. Batchelder, which has matured into Patent 2,383,362, grantedAug. 21, 1945, and Serial Number 370,608 filed December 18, 1940 byE/ldwin L. Hall and Howard R. Batchelder, there are,de scribed andclaimed processes for the separation of such petroleum oil tar emulsionsinto the water, residual tar and hydrocarbon oil without polymerizationor with greatly reduced polymerization of heat polymerizable unsaturatesin the tar and with the recovery of greatly increased yields ofhydrocarbon oil boiling within the range of from 210 C. to 350 C. andhigher, said oil being substantially free of'intensely colored pitchconstituents which comprise residual tar and containing relatively largequantities of heat polymerizable monomeric unsaturated hydrocarbons ofraromatic characteristics.

The said copending application 342,735 discloses the separation ofpetroleum oil tar emulsions and the separation of "dead oil and lightoil" from the pitch constituents of residual tar by rapid distillationwith the avoidance of polymerization of dead oil" constituents.

The said copending application 353,034 discloses the separation ofpetroleum oil tar emulsions and the separation of dead oil and light oilfrom the pitch constituents of residual tar by the use of relativelylow-boiling hydrocarbon solvents such as propane, butane, etc. with theavoidance of polymerization of dead oil constituents.

Copending application 370,608 discloses other methods for suchseparation such as fractional condensation.

Copending application 370,608 also describes and claims the heatpolymerizable monomeric hydrocarbons produced by such separationprocesses and heat polymers produced therefrom.

I have found that new and valuable resins may be produced bycatalytically polymerizing unsaturated hydrocarbons boiling within therange of from 210 C. to 350 C. and higher, said material boiling Withinsaid boiling range having been separated from petroleum oil tar by aprocess such as the processes described and claimed in 4 the abovecopending applications in which excessive polymerization of heatpolymerizable monomeric hydrocarbon material in said boiling range isavoided. v

Thus, whereas in the conventional separation of dead oil from petroleumtar emulsion, namely by extended distillation lasting frequently up tohours and more, very little if anyheat polymerizable monomerichydrocarbon material is taken olf in the dead oil boiling range, in mystarting materials such heat polymerlzable monomers are present to atleast 15% of the total unsaturation present in the dead oil andpreferably to at least I As catalysts, I profer to employ acid actingcatalysts such as mineral acids, for example, sulfuric acid, hydrogenchloride, acids of ,phosphorus, or acid acting metallic halides orcomplexes of said halides, preferably organic solvent complexes, as forexample, boron triuoride, aluminum chloride, boron trifluoride-diethylether complex, boron trifluoride-dimethyl ether complex, borontriiluoride-phenyl ethyl ether com-v plex, boron triuoride-phenyl methylether complex, boron trluoride-dioxan complex, boron trifiuoride-toluenecomplex, corresponding aluminum chloride complexes, etc.`

Metallic halides and their complexes, which I may employ asI catalyst,are characterized by their ability to hydrolyze in the presence of waterto give an acid reaction and, hence, for convenience they may be termedacid acting metallic halides.

Though 'acid -acting catalysts are preferred, other catalysts may beemployed if desired such, for example, as catalysts of the neutralsurface type. Examples of such catalysts are activated clays, silicagel, activated carbon, etc.

In carrying out my invention, I prefer to divide the hydrocarbon oilseparatedfromrresidual tar into light oil boiling up' to approximately210 C. at atmospheric pressure and dead oil boiling above 210 C. atatmospheric pressure. This division may be made by distillationpreferably under vacuum or in the presence of a diluent such as'steam,to reduce the partial pressures of the constituents in 'order to avoidexcessive heat polymerization during the separation of the material intolight oil and dead oil.

I have discovered that by far the greater proportion of the totalunsaturation contained in the dead oil So obtained may be catalyticallypolymerized to produce high yields of new and valuable resins.

I have further discovered that the total, unsaturation is comprised ofaconsiderable portion readily polymerized either by heat or by a catalystand a considerable portion readily polymerized `by a catalyst but notreadily I Jolylmrerized.by heat. Y

There appears to be a tendency for the. material which is readilypolymerized by heat toconcentrate in the higher boiling portion' ofthedead oil, whereas the material readily polymerized only by a catalystappears to have a tendency to concentrate in the lower boiling portionof the dead oil.

The foregoing features aswelllasvotherfeatures of the invention will bemore particularly described as the specification proceedaand inconnection with the attached figures in which:

Figure l shows curves illustrating unsaturation in, cuts of dead oil;and .y

Figure 2 shows curveskllustrating alrelation between total unsaturationand polymeryield from various dead oil cuts.y Q

As an example of la convenient procedure for the production of mymnewpolymer with the, use of sulfuric acid as catalyst, the 'following lisgiven.

y f s Example v1 l .VA sample of theoilvto be'polymerized, say 500 cc.is poured into a two-liter B-neck ask equipped with a thermometerandlstirrer. To the oil is addedf 96% H2SO4y f whilev agitatingvigorously. Thea'cid is added l cc. at a time and the tempera- .turev is-not' permitted to exceed ,50",y C., v control being obtained by raisingor loweringan ice water bath. The addition of the acid is continued inthis manner until no further temperature rise is noted. Usually thenecessary amount of acid to achieve this end has been found by volumeofthe oil present. s ,Y

' The oil is then diluted withfapproximately van equal volume ofriaphtha, toluene, or similardiluent and the solution then decanted into500 cc. of warm water (approximately'SOCJ, leaving the acid sludgebehind.` l 'y to be 'about 1% After settling the water layer is drawnoff and neutralization of the acid is accomplished by use of a to 20%NaOH solution. After the caustic washing an additional water wash may bemade. Whether the additional water wash is employed or not the resinsolution is dried by filtration through a bed of a drying agent such aslime.

If desired, the diluent may be added before polymerization instead ofafter polymerization.

After neutralization and drying the resin may be extracted, that is,removed, from the unpolymerized oil or the resin may be concentratedtherein by vacuum distillation which may be assisted by steam. 'I'hemelting point of the resin and the yield will depend, other things beingequal, upon the degree of extraction of the resin from the unpolymerizedoil.

An extraction procedure which has been found convenient particularly inthe determination of resin yields is as follows:

Example 2 The material is transferred to a tared two-liter ask equippedwith a ground glass neck. The material is carefully weighed at thispoint.

The flask is provided with means for measuring vapor temperatures and isconnected with condensing apparatus and with means for providing avacuum including a pressure control device.

(1) Bumping during distillation is avoided by folding iron Wire severaltimes to such length that one end reaches slightly into the neck of theask while the other rests on the bottom of the ask.

(2) The pressure is reduced to 100 mm. Hg absolute and heat is appliedby means of a bunsen burner.

The distillation is continued at 100 mm. Hg absolute pressure until thevapor temperature reaches 180 C. During the first stage of thedistillation care should be exercised to prevent crystallization ofnaphthalene if present, as by operating the condenser at a temperaturesufliciently high to avoid this.

(3) When the vapor temperature reaches 180 C. at 100 mm. Hg absolute,the flame is lowered and the pressure gradually reduced to mm. absolute,using care to avoid carry-over. When a pressure of 20 mm. Hg is reached,the pressure is maintained at that value and the distillation continueduntil a vapor temperature of, for example 195 C., is reached.

During this second stage the condenser may be cooled by cold watertaking care to avoid the solidication of anthracene, if present.

The distillation is conducted rapidly, 5 to 10 cc. of oil per minutebeing taken off.

When a Vapor temperature of 195 C. is reached heating is discontinuedand air is allowed to enter the apparatus slowly until atmosphericbalance is restored.

The flask is then disconnected, the Wire removed and the flask with theresin weighed.

The percent yield of resin is calculated as follows:

MXIOO=% resin at the melting Ongmal 011 Welght point of the resin asobtained.

use of steam during the distillation. Lower melting point resins may beproduced by terminating the distillation at lower temperatures.

Although various methods for determining melting points are availablefor convenience and reproducibility melting points as set forth in thisspecification are intended to mean melting points as determined by thecube in mercury method using apparatus described in A. S. T. M.Designation D 61-24 with the following modifications.

1. Mercury is employed in depth of 2% inches instead of water.

2. The cube of resin is rigidly supported by clamping the hook uponwhich the resin is attached so that the top of the cube is 1 inch belowthe surface of the mercury.

3. A 11/2 inch immersion thermometer is employed and is immersed to thatdepth.

4. The exact temperature at which the resin becomes visible at thesurface of the mercury is recorded as the softening point of the resin.

5. The melting point of the resin is calculated from the softening pointby the following formula.

Melting point C.=Softening point C. 1.25+2 C.

As before stated, lower or higher melting point resins may be obtainedby varying the extraction of associated oil. Thus resins ranging fromvery soft to hard resins having high melting points may be readilyobtained.

It has been found that as a general rule each 6% of oil left in theresin lowers the melting point about 10 C.

Resins having calculated C. cube in mercury melting points have beenreadily produced in yields of from 26% to 37% of dead oil obtained inthe process of copending application Serial Number 342,735, and resinsof the same calculated melting point in yields as high as 53% have beenobtained in the case of dead oil obtained in the process of copendingapplicatio Serial Number 353,034. y

Actual yields with melting points less than 120 C. may be readilyconverted to calculated yields at 120 C. melting point by subtractingfrom the actual yield in per cent apercentage of the actual yield in percent equal to 120 C.-actual melting point C. l0

Conversely yields of resin with melting points greater than 120 C. maybe converted to calculated yields at 120 C. melting point by adding tothe actual yield in per cent a percentage of the actual yield in percent equal to Actual melting point C.-120 C. 10

Unless otherwise stated, yields of resins given herein are yieldsconverted to 120 C. melting point.

The color of the resins obtained hereunder vary from light yellow todark brown depending upon the particular material polymerized and otherconditions.

For convenience resins obtained in accordance with the present inventionhave been rated in color in accordance with the following colorcomparison method.

Color standards are kept in 'l oz. French square glass stoppered bottlesand are sealed to prevent evaporation.

Three stock solutions are prepared.

No. Solution A Solution B Solution C Water M1. M. Mt.

0. 9 0. 7 2. l. 5 2. 8 l. 9 4. 0 2. 5 5. 3. 2 8. 0 4. 0 13. 0 5.0 16. 04. 0 250. 0 20. 0 5. 5 200. 0 8. 0 2. 0 40. 0 16. 0 3. 0 40. 0 26. 0 2.0 20. 0 50.0 4. 0 1l. l 50. 0 4. 0

Fractional standards may be prepared as Iollows:

` No. Pipette 50 ml. of No. 1/2 into a 100 ml. volumetric flask anddilute with Solution A to 100 ml Repeat the above procedure except use50 ml.

of No. 1A instead of 50 ml. of No. 1/2 1/8 Repeat the above procedureexcept use 50 ml.

of No. 11/2 3A Repeat the above procedure except use 50 ml.

of No.' 1%;

In the color determination of a resin, 2 grams of the resin aredissolved in 25 cc. or 21.7 grams of water white toluol. When solutionis cornpleted it is then transferred to a 7 oz. French square glassstoppered bottle of the same dimensions as the standard, and the colorestimated by comparison Awith the standards.

In the event the color of the solution prepared in this manner is darkerthan color standard No.

10, 1 cc. of the resin solution is made up to 26 cc.

with additional toluol. A suitable quantity may then be transferred to aFrench square glass stoppered bottle and the color estimated bycomparison with the standards. Due to the fact that the resin solutionhas been diluted with additional toluol 10 will be added to 'theobserved color reading in this case. If this second sample is stilldarker than No. 10 standard another dilution is performed in exactly thesame manner. In this latter case 20 will be added to the observed colorreading.

Resins obtained hereunder have been produced with colors ranging fromand below to 19 and above according to the above described method ofestimating color.

Resins obtained hereunder produced from dead oil obtained in accordancewith copending application Serial Number 342,735 have shown a tendencyto be somewhat lighter in color than those produced from dead oilobtained in accordance with copending application Serial Number 353,034.Also my resins when produced from the lower boiling portions of dead oilthus obtained have shown a tendency to be somewhat lighter in color thanmy resins when produced from the higher boiling portions.

Further. my catalytic resins, generally speaking, have shown a tendencyto be somewhat lighter in color than heat polymer resins produced fromthe same oil although this is not always true.

Convenient procedures for the production o! my new polymer with the useoi metallic halide catalysts or metallic halide-orgamc solvent complexcatalysts is as follows:

E'Illmple 3 5 10 grams oi' the selected catalyst is suspended in 300 cc.of benzene by stirring. 300 cc. of dead oil to be polymerizcd are addeddropwise from a separatory funnel while maintaining the temperature ofthe reaction mass below 50 C. by raising or lowering an ice water bathas needed. When the addition is completed the mass is stirred for 2hours and then neutralized with aqueous NaOH solution (10 to 20%).Stirring is continued for an additional hour. Clay or other filter aidis added and the mass is subjected to suction filtering. The aqueouslayer is then separated and the treated material is washed with hotwater until neutral to litmus. The treated material is then filteredthrough lime to remove H2O, and the resin is then extracted fromassociated oil as previously described.

Example 4 10 grams of the selected catalyst is suspended by stirring in200 cc. of dead oil to be polymerlzed. An additional 300 cc. of the deadoil is then added dropwise from a separatory funnel while maintainingthe temperature of the reaction mass between 40 C. and 60 C. When theaddition is completed the mass is stirred for 2 hours. 500 cc. ofbenzene is then added. The mass is then neutralized with aqueous NaOH(10 to 20%) while continuing the agitation for an additional hour. Clayor other filter aid is added and the mass subjected to suctionfiltering. The caustic aqueous layer is separated and the treatedmaterial is then washed with hot water until neutral to litmus. Thetreated material is then filtered through lime to dry and the res'm isthen extracted from `the associated oil as previously described. I

'I'he following example shows results obtained on dead oil separatedfrom distillate recovered from petroleum tar emulsion by flashdistillation as described in copending application Serial Number342,735. The polymerization procedure of Example 1 was employed.

Example 5 506.2 grams of dead oil in solution in toluene were treatedwith 5 cc. of 66 B. HzSOt. Approximately 37% of the dead oil wasconverted to resin having a melting point of 98.2 C. and a color of 13.The end temperature of the distillation for removal of oil from theresin-was 185 C. and the end pressure was 20 mm. Hg. 267.7 grams of oilwere recovered. The calculated per cent yield of C. melting ypoint resinwas 32.3%.

In the following example dead oil obtained as in Example 5 was subjectedto steam distillation after separation from the light oil, but beforepolymerization,` to remove heat polymers formed during the separation oflight oll. The polymerization procedure of Example 1 was employed.

Example 6 499.4 grams of dead ou were treated with 4 cc. of 66 B. H2SO4.Toluene was added after polymerization. Approximately 33% of the deadoil was converted to resin having a. melting point of 105.8 C. and acolor of 9. The end temperature of the distillation for the removal ofoil from the resin was 185 C. and the end pressure was 20 mm.

culated per cent yield of 120 C. melting point resin was yapproximatelyIn the following table are given the results of a series ofpolymerizations in which metallic hal- Hg. 293.4 grams of oil wererecovered. The cal- 5 ide type catalysts were employed following theculated per cent yield of 120 C. melting point general procedure ofExamples3 and 4. T he dead resin was 30.1%. oil was of the type obtainedby flash distillation The dead oil employed in the following examplefollowing the procedure of copending application was extracted frompetroleum tar emulsion along Serial Number 342,735.

Table 1 scarti Yi ld t mmleiiIt Pmflt Catalyst dead gli renitil :gsinpzgbelge on cgto 0122K), Remarks ing. g. orig. 120 C.

dead oil M. P.

.1 96.5 108.8 31.9 29.7 17 Solvent present. .2 183.8 144.7 36.6 42.2 17Nc solvent. .o 109.1 106.4 86.4 33.3 15 steamdistillcd cil. .2 193.9120.1 38.9 88.9 15 Nc solvent. .7 85.4 151.0 28.6 33.9 14 Solventpresent. .4 173.9 140.0 35.0 40.5 1a Nc solvent. no .4 159.2 113.9 81.980.8 8 steam distilled cil. .1101113110 .5 185.2 129.0 37.0 39.0 14 Ncsolvent.

with light oil following the procedure described in From the foregoingit will be seen that mixed copending application Serial Number 353,034.catalytic polymers of monomeric hydrocarbons After separation of thelight oil the polymerizareadily polymerizable by heat and of monomeriction procedure of Example 1 was followed. hydrocarbons not readilypolymerizable by heat Example 7 are produced except when heatpolymerizable resins are removed prior to the catalytic poly- 532.6grams 0f dead O11 Were treated 8 CC. 30 merization of the remainingmgnomeric matof 66 B. HzSOl. Toluene was added after polyriaLmerization. Approximately 42% of the dead oil I have found thatgenerally speaking, the unwas converted to resin having a meltingP01111? 0f saturation in dead oil of the general type treated 97 C. anda color 0f 17. The end temperature 0f herein is unevenly distributed inthat it tends the distillation OI' the removal Of Oil from the 35 toconcentrate in the lower and upper boiling resin was 192 C. and the endPressure Wes 18 mmranges of the dead oil with a relatively lower con-Hg. 145.9 grams 0f Oil were recovered. The calcentration of unsaturatesin the middle boiling culated per cent yield of 120 C. melting pointrange. resin was 36.2%. A typical distribution of unsaturation and Inthe following example the dead Oil 0f EX- 40 other characteristics isshown in the following ample? Was Steam distilled just prior t0polymeltable in which are set forth the properties of ization t0 remOVeheat Polymer formed during cuts produced by the distillation of dead oilde- S separe-H011 from light oil. The polymerizarived from petroleum taremulsion by the method tion procedure 0f Example 1 was followed- 45described in copending application serial Num- Eample 8 ber 342,735. Tble 2 504 grams of dead oil were treated with 6 cc. a of 66 B. H2SO4.Naphtha was added after polyi- A t Percent V merization. Approximately27% of the dead ol pprOXlma. e item1 50 apt. was converted to resinhaving a melting point of 5o Cut No' eofalmlg. untu @9310?? Ei.' 119.4C. and a color of 14. The end temperature to C. mm. l; pressure of thedistillation for thel removal of oil from the resin was 225' C. and theend pressure was 20 150@75 14.3 0.9672 5.68 218 mm. Hg. 303.5 grams ofoil were recovered. The 1595@ 75'160 139 19789 L54 227 calculated percent yield of 120 C. melting point 161715@ 75-170 14.1 0.9872 3. 74 23gresin was also approximately 27%.

The dead oil of the following example was ob- 178).@ 75427@ 13'6 0'99313'10 249 tained from .petroleum tar emulsion by the proc- 6 {jg i: gggess of copending applicatlon Serial Number 7...- 164@8200@8 9.7 1. 05774.45 327 342,735. After separation from light cil it was G0 Remue 7-5treated to remove heat polymerizable unsaturates by heating at 200 C.for 4 hours followed by removal of the heat polymer resin formed. It wasthen subjected to catalytic polymerization following the procedure ofExample 1.

Example 9 Each of the cuts of Table 2 was divided into two portions. Oneportion was heat polymerized for four hours at 200 C. according to themethod described in copending application Serial Number 370,608, whilethe other portion was catalytically polymerized with approximately 1% byvolume of 96% H2SO4 followed by neutralization and washing according tothe procedure of Example 1.

After polymerization each resin was hardened by vacuum distillation ofoil from the resin.

The following table shows the yields and colors of the resin producedfrom the various cuts by the two methods of polymerization,

Table 3 Table 5 Catalytic (H130.) Solvent oll Solvent oil Heatpolymerization Polymerization Original oil from heat from acid 5 ont NQ.polymer polymer Cut No' Percient Percent Percent Percent 1 a 1 a l a rcsn resin resin res correctid based ci? 0.91m' coirzlzcutl baiiied can" lo to or o to ong g 37.9 36. 9 24. 3 23. 7 1. 45 1. 41 3l. 7 31.3 23.823.4 1. 17 1.06 19. 4 2. 77 13 36. 2 5. 1S 6 26. 9 26. 7 17. 9 17. 8 90.88 10. 3 1. 43 2G. 9 3. 74 9 24. 2 24. 5 14. 8 14. 5 1. 12 1.14 10.4 1. 47 9 27. 3 3. 86 9 26. 2 27. 2 12. 7 13. 2 1. 52 l. 68 11. 6 1. 5810 23. 6 3. 21 14 35. 0 39. 5 l5. 0 10. 9 3. 52 3. 96 19. 2. 66 14 28.03. 81 14 37. 4' 49. 4 23. 0 30. 3 23. 4 30. 9

21. 4 2. 08 14 10. 2 99 14 jjjjjjjjj Dark 35139 :jjj: 15 It will be seenthat only in cut 1 do the different methods of arriving at molecularweight in- After extraction of the resin the recovered oils wereexamined as to density and unsaturation with the following results.

In order to calculate the per cent of the unsaturation in the above cutsit was necessary to assume (1) the molecular weight for each cut; and(2) that each unsaturated molecule contains a definite number of doublebonds.

The molecular weights of the above cuts were calculated by two methodsand the results are shown in Figure 1 in which molecular weight and 50%boiling points of the cuts are plotted as ordinates against per cent oftotal dead oil as the abscissa.

In curve I it is assumed that cut I consists predominately ofnaphthalene and methyl indene with anaverage molecular weight of 129,while out 'I is assumed to consist predominately of com pounds havingthe molecular weight oi' anthracene, namely 178. Intermediate cuts areassumed to have intermediate molecular weights falling on a straightline.

Curve 2 is a plotting of the 50% boiling points of tbe various cuts.

Curve 3 is a plotting of the mean molecular weight of each cut on theassumption that the mean molecular weight of a cut is a function of the50% boiling point of the cut and, hence the curve 3 will be a parallelto curve 2. The exact relation of curve 3 to curve 2 was takenempirically from consideration of the rst ilve cuts.

Table 5 shows the unsaturated content of the original cuts and theunsaturated content of the oil extracted from the respective resins inthe case of heat polymerization and in the case of sulfuric acidpolymerization. In each case, the column headed 1 is the unsaturationcalculated in accordance with the. assumptions underlying curve I ofFigure 1 and the column beaded 3 is the unsaturation as calculated fromthe assumptions underlying curve 3 of Figure 1. In both cases it isassumed that there is but one double bond per molecule.

troduce significant diierences in the calculated unsaturations.

Referring to Figure 2, in this figure are shown curves in which per centof resin produced or calculated in the casevr of each cut is plotted asthe ordinate against per cent of total dead oil as the abscissa.

Curve 4 shows the possible yield of resin assuminer that the totalunsaturation as indicated in curve I of Figure 1 is polymerized. Curve 5shows the possible yield of resin assuming that the total unsaturationas calculated in accordance with curve 3 is polymerized.

Curve 6 shows the yield of resin actually obtained by sulfuric acidpolymerization of the various blended cuts.

Curve 'I shows the actual resin yield produced by heat polymerization ofthe various blended cuts.

From the curves and the other data on the polymerization of dead oilcuts the following may be noted.

The first cuts and the last cuts contain the most unsaturation withlower unsaturations in `the middle cuts.

The acid polymer yields more nearly approach the calculated resincontent than do the heat polymer yields.

Heat polymerizes a smaller proportion of the total unsaturates in thelower boiling cuts than in the higher boiling cuts.

The minimum resin yield for heat polymers falls in a lower cut than theminimum resin yield for acid polymers and also falls in a lower cut thanthe minimum unsaturation content as determined by Bra numbers.

In the lower boiling fractions the density of the oils recovered fromheat polymers is higher than the density of the original oils, while inall f Aother cases the density of the recovered oils is eitherapproximately the same or is appreciably lower than that of the originaloils.

From the viewpoint of the color of the resulting resins, it may bepreferable to acid polymerize the lower boiling fractions of the deadoil and heat polymerize the higher boiling fractions.

On heat polymerization of a sample of the original oil prior tofractionation into cuts, a yield of 23.2% of heat polymer was securedwhich compares very closely with the total of 22.28% for the total ofthe heat polymers from the cuts.

On sulfuric acid polymerization of the original oil prior tofractionation, a yield of 37.1% acid polymer resin was secured. This issomewhat higher than the total of 33.09% from the various cuts. It willbe noted that the acid resin yield from cut i is very low. It is thoughtthat this might have been due to cracking during the fractionation ofthe oil into cuts. The cracking may have produced inactive unsaturation.

In another test made on a similar basis but with somewhat different'fractionation procedure The overhead material yielded 26.2% of resinhavingv a. color lOi 9 when polymerized by sulfuric acid in accordancewith the before described method.

the acid polymer from the high boiling cut did The residue yielded 41.7%resin having a color not fall oil. in the manner shown in curve 6 of of16 when polymerized by thermal polymeriza- Figul'e 2- tion at 200 C. forfour hours.

AS an example 0f the division 0f the dead 011 These yields correspond toan overall yield of intotwo PortlOPS and the acid polymerization 32.7%as compared with approximate yields of of the lower bolling portion andthe heat polyl0 24% by thermal polymerization of theventire merlzatin 0fthe higher boiling 901111011, the f01 dead ou and about 35% by acidpolymerization lowing may be givenv of the entire dead oil.

Example 10 I have found that the acid polymers are much Two 1000 gramssamples of dead oil produced gli; silhble flhanlvheatt polymrhfmin gielSame as described in copending application Serial o n a 5 en s excel ea' co s' Number 342,735 were distilled 1n vacuo until I furthe foundthat polymers from dead ons 57.8% came overhead leaving a residuen: 422%obtained from the rapid distillation process of The separatedistillation Of a 100 cc. sample ct)Pending application .Serial Number3421735 f the distillate and of a 100 cc. sample of the 20 tend to bemore soluble in those solvents tried residue showed the following. thansimilarly produced polymers from dead oils Table 6 produced in thesolvent extraction process of copending application Serial Number353,034. The greatest increase in solubility of the acid mstma CResidue'tc' 25 polymers as compared with the heat polymers is noted withsuch solvents as acetone and diethyl ether but substantial increases insolubility are also to be noted with petroleum solvents. The followingtable shows typical solubilities of various sulfuric acid polymers ascompared speelse gravity 120 O. 0994 With heat DO lYYFerS- Viscosity at100F The solubllltles are expressed in grams dlssolved per 100 grams ofsolvent.

Table 7 Y i Sunoco Stoddard! Etnl DltlllllFlthl 'r alcolisti] etellery'lslcgglslr acctaxte Atone CCI ltgn Toluege gl; (822:35

HEAT POLYMERs OF DEAD olLs FROM FLASH Dls'llLLA'llON OF TAR Resinmeltlng pelnt195 O 0.17 1.22 0.22 3.13 1.01 .04 10. 45 39.33 2.55 2.21Resin melting pelnt112 O 0.20 1.23 1.10 54. 71 2.40 43.32 45.40 102.9732.72 3.40 Resinme1tlngpeint91 O 0.55 5.37 0.30 125.25 4.12 .99 34.46170.06 29.70 0.71

HEAT POLYMERS `OF DEAD O1L FROM PROPANE EXTRAOTION OF TAR Resin meltingpeint134 O 0.13 0.27 0.57 2.02 1. 43 49.15 13.10 53.74 5.43 3. Resinmeltmg peint 115 c 0.00 2. 79 0.00 2.10 1.07 53.00 34.20 32.97 5.21 7.Resin melting peint C 0.09 1.33 0.73 0.32 3.20 72.49 29.30 144.40 3. 582.

mso. POLYMER OF DEAD OIL FROM FLASH DISTILLATION OF 'FAR Resin meltingpoint C 0.73 193.05 3.09 130. 34 117.13 105.65 49.52 154.01 44.91 49. 35Resin melting peint 109 O 0.94 139.00 4.90 123.50 133.34 42.33 52.43153.30 100.57 51.50

mso. POLYMER OF DEAD OIL FROM PROPANE EXTRAOTION OF TAR Resin meltingpeint 107 O 1.44 12.39 3.10 112.02 12.30 05.53 46.25 105.09 10.40 9.34

H1801 POLYMER OF STEAM DISTILLATE FROM DEAD OIL FROM FLASHDrs'rlLL'ATION OF TAR Resin melting point 106C .0.73 t 152. 72 3.3593.24 111.47 53.50 89.39 142.15 52.22 n 47.51

H1804 POLYMER 0F STEAM DISTILLATE FROM DEAD OIL FROM PROPANE EXTRACTIONOF TAR vResin melting point 119 C 0. 83 152. 03 5. 01

sulfuric acid resinsfrom dead oils from ila-sh distilled and propaneextracted tars as compared nwithheat polymers from dead oil from flashdisasoma? but a slight diazo reaction indicating the substantial absenceof phenols.

The resins of this invention usually will give negative Lieberman Storchreactions indicating tilledand propane extracted tars. absence of rosinacids.

Table 8 Percent 1 Percent in- Percent solu- Percent-solu- Percentnsoluble in gblti Percent ggg? ggg: 13? g: Ccuclgd Total Type oi solublein etroleum kum heb soluble in 1 umgther leumether sti'uems soft.=Source oidead oil polymertroleum et er-pentane Demme and pcntaneeNotex Extracted' (calculated and zaticn et er-pcntane but soluble CCM (canpetroleum u, ed fr m from cla from M 'P hard (asphaltenes) in C014 ethera o y resins (hud resins) benes and clay (soit (oily constiof resins)carboids) resins) tuonts) Dead hiiiron'i Hash Heat 40.5 40.5 0. 02 59.4A 26.5 32.9 51.0 06. 5 ,l dist e tar. Dead oil fromdltn'odo 48.4 19.127.3 53.5 14.2 .39.3 43.2 33.3 Y.. ane extracte .an Dad .iildftromlflash Suliiric l0. 6 10. 5 0. 03 89. 3 44. 3 45. 1 49. 8 64. 8 A:Visi eai". aci .'Dcad oil iromprodo. 63.4' 53.2 0.1 46.6 8.9 37.7 46.8 62. l f'pane extracted tar.

Themethod generally followed in tests for solubility showniin Table 8 isthat described in "Asphalts and Allied Substances-Herbert AbraharnflthVedition published by O. Van Nostrand CoChapter `32,` Subsections 38a to38C inclu- Vysive;particularly page 1008. CC14 was employed instead of'CHClsi NogreatI difference has been observed in the molecular weight ofthe resins of equal melting point produced hereunder regardless of themethodlofl polymerization. Naturally, the molecular weight of the resinvaries Widely with the degree of extraction of associated oil as doesthe melting point. Highly extracted resins have high melting points andhigh molecular Weights, while resins less-exhaustively extracted havelower melting ,points and lower molecular Weights.

Molecularvweights from a large number of catalytic resins hereunder werefound to vary from 354 for resin melting at 94 C. (cube in Hg) to 629for aresin having a melting point of 151 C- (cubeinHg). Y The molecularweights were determined by the benzene freezing point depression method.

VThe densities of' the acid polymers tend to be somewhat lower-than theheat polymers from the same dead oil. vThus sulfuric acid polymers fromdead oils from the flash distillation of petroleum tar have been' notedto vary from 1.12 to 1.13, while heat polymers from dead oil of thistype have been noted to=vary from 1.14 to 1.16.

The sulfuric acid polymers from dead oils from the solvent extraction`of petroleum oil tar have been noted to be somewhat higher in densityfor example, of the order of 1.18 and higher. Heat resins from the deadoil from the same type of solvent extracted tar have been found to varyfrom 1.15 to 1.20. l

AlCh polymers examined. have had densities varying from 1.12 to 1.14.

BFaEtzO `polymers have been noted to have densities of the orderfof 1.25to 1.31.

From the densities and other characteristics of the resins and .of theassociated oils, these materials are evidently of a `highly aromaticnature.

:The resins of this invention, except those hardened by exhaustive steamdistillation to Va very high melting point, will usually reactpositively in the anthraquinone reaction indicating the presence ofanthracene, unless produced from lower boiling portions of the dead oil,which do not contain anthracene, or unless the anthracene were otherwiseremoved.

The resins of this invention will usually give On thermal decompositionof the resins of this invention, appreciable yields of material boilingwithin the range from 210 C. to 350 C., will be produced.

Th'e catalytic polymer resins of this invention are usuallysubstantially completelysoluble in CS2 and 2 Benzol.

The processes described in the above copending applications are examplesof methols for deriving dead oil" unsaturated hydrocarbon material whichmay then be polymerized by methods such as are described herein. Otherprocedures for deriving deadoil unsaturated material,

.- however, might be employed. 'I'he important factor in this respect isthe separation of the dead oil from the residual tar without prolongedheating in contact with the pitchy materials of the residual tar. Statedin other words, th'e greater the extent to which polymerization of thesedead oil materials into the residual tar is avoided, the higher will bethe yield of high ,boiling heat polymerizable and also catalyticallypolymerizable monomeric material.

After separation of the dead oil from the residual tar avoidance ofpolymerization is not so important if it is desired to convert this heatpolymerizable monomeric material into heat polymers as any such polymersmay be separated from the "dead oil by distillation.

However, if the highest yields of catalytic polymer are desiredavoidance of excessive heat polymerization after separation from theresidual tar is also desirable.

The particular yields of catalytic polymers will depend, otherconditions being equal, upon the character of the petroleum oilpyrolyzed and the conditions of pyrolysis. Higher yields are usuallypossible in connection with the pyrolysis of the more naphthenic oilsfor instance, oils of classes 5 to 7 as determined by the method ofclassification of Bureau of Mines Bulletin #291 as modified by BureauofMines Report of Investigations 3279, with oils of class 7 the morepreferred. Temperatures of pyrolysis above 14.50 F. may be preferredalso from a standpoint of yields of resin.

In the separation of lower boiling hydrocarbon material from the pitchconstituents of residual tar by various methods, the oil separated maycontain components boiling above 350 C. and/or below 210 C. and it isnot intended generally to preclude the presence of catalyticallypolymerizable monomeric material boiling outside the range of from 210and 350 C. with the monomeric material boiling within that range nor isit intended generally to preclude the presence of catalytic polymersderived from monomers boiling outside said range along with polymersderived from .5

monomers boiling within said range.

Examples of procedure and characteristics above described are given forpurposes of illustration. It is not intended that the invention shall benecessarily limited thereby.

The catalytic resins produced hereunder are of value in the productionoi paints, enamels, lacquers, rooting compounds, friction materials,such as brake blocks and brake liningsl coating for coal to preventdusting, printing ink, paper, caulking compounds, etc. I

The associated oils recovered in the extraction of the resins are highlyaromatic and valuable as high boiling solvents.

The addition of other materials to the cataiytically polymerizablemonomeric unsaturated materials prior to polymerization or to the resinsafter polymerization may, of course, modify the properties oi the resinproduced.

Examples of such materials are other synthetic or natural resins,plasticizers, softeners, fillers,

coloring materials, etc. vWhile I have referred to a certain type ofunsaturated monomeric hydrocarbon material as being polymerizable byheat and by catalysts, it is to be understood that either or both may beapplied.

These and .other modications may be made without departing from thespirit of this in.

vention.

I claim: 1. A process for producing a hydrocarbon resin from ahydrocarbon oil which has been physically separated from tar produced inthe vapor phase pyrolysis of petroleum oil and which is free from and ofgreater volatility than the pitch of said tar, said hydrocarbon oilcontaining in addition to hydrocarbons boiling between 210 C. and 350 C.which are not polymerizable by the application to said oil of heat alonebut which are polymeriztreating said oil with a resin-producing catalystbut which last-mentioned hydrocarbons are also polymerizable to heatresin polymer by the application to said oil of heat alone, saidlast-mentioned hydrocarbons being present in said hydrocarbon oil inamount greater than approximately 15% of the total unsaturation presentin said hydrocarbon oil boiling between 210 C. and 350 C. as determinedby bromine titration, comprising polymerizing in admixture both types ofsaid polymerizable hydrocarbons contained in said hydrocarbon oil toform catalytic resin polymer by treating said hydrocarbon oil with aresinproducing catalyst.

2. A process for producing a hydrocarbon resin from a hydrocarbon oilwhich has been physically separated from tar produced in the vapor phasepyrolysis of petroleum oil and which is free from and of greatervolatility than the pitch of said tar, said hydrocarbon oil containingin addition to hydrocarbons boiling between 210 C. and 350 C. 70

which are not polymerizable by the application to said oil of heat alonebut which are polymerizable to catalytic resin polymer by treating saidoil with a mineral acid catalyst. other hydrocarbons boiling between 210C. and 350 C. which are polymerizable to catalytic resin polymer bytreating said oil with a mineral acid catalyst but which last-mentionedhydrocarbons are also polymerizable to heat resin polymer by theapplication to said oil of heat alone, said last-mentioned hydrocarbonsbeing present in said hydrocarbon oil in amount greater thanapproximately 25% of the 3. A process for producing a hydrocarbon resinfrom a hydrocarbon oil which has been physically separated fromtar-water emulsion produced in the vapor phase pyrolysis in the presenceof steam or' petroleum oii and which is free from and of greatervolatility than the pitch of said tar, said hydrocarbon oil containing1n addition .to aromatic hydrocarbons boiling between 210 C. and 350 C.which are not polymcrizable by the application to said oil oi heat alonebut which are polymerizable to catalytic resin polymer by treating saidoil with suli uric acid, other aromatic hydrocarbons boiling between 210C. and 35u C. which are poiymerizable to catalytic resin polymer byltreating said oil with sulIuric acid but which last-mentionedhydrocarbons are also poiymerizaoi'e to heat resin polymer by theapplication to said oil of heat alone, said last-mentioned hydrocarbonsbeing present in said hydrocarbon oil in amount greater thanapproximately 25% of the total unsaturation present in said hydrocarbonoil boiling between 210 C. and 350 C. as determined by brominetitration, comprising polymerizing in admixture both types or saidpolymerizable hydrocarbons contained in said hydrocarbon oil to formcatalytic resin polymer by treating said hydrocarbon oil with sulfuricacid.

4. A process for producing a hydrocarbon resin from a hydrocarbon oilwhich has been physically separated from tar-water emulsion produced inthe vapor phase pyrolysis in the presence of steam of petroleum oil andwhich is free from and of greater volatility than the pitch of said tar,said hydrocarbon oil containing in addition to hydrocarbons boilingbetween 210 C. and 350 C. which are not polymerizable by the applicationto said oil of heat alone but which are polymerizable to catalytic resinpolymer by treating saidoil with an acid-acting metallic halidecatalyst, other hydrocarbons boiling between 210 C. and 350 C. which arepolymerizable to catalytic resin polymer by treating said oil with anacidacting metallic halide catalyst but which lastmentioned hydrocarbonsare also polymerizable to heat resin polymer by the application to saidoil of heat alone, said last-mentioned hydrocarbons being present insaid hydrocarbon oil in amount greater than approximately 25% of thetotal unsaturation present in said hydrocarbon oil boiling between 210C. and 350 C. as determined by bromine titration, comprisingpolymerizing in admixture both types of said polymerizable hydrocarbonscontained in said hydrocarbon oil to form catalytic resin polymer bytreating said hydrocarbon oil with an acid-acting metallic halidecatalyst.

5. A process for producing a hydrocarbon resin from a hydrocarbon oilwhich has been physically separated from tar-Water emulsion produced inthe vapor phase pyrolysis in the presence of steam of petroleum oil andwhich is free from and of greater volatility than the pitch of said tar,said hydrocarbon oil containing in addition to aromatic hydrocarbonsboiling between 210 C. and 350 C. which are not polymerizabie by theapplication to said oil of heat alone but which are polymerizable tocatalytic resin polymer by treating said oil with activated clay, otheraromatic hydrocarbons boiling between 210 C. and 350 Cz" which arepolymerizable to catalytic resin polymer by treating said oil withactivated clayl but which last-mentioned hydrocarbons are alsopolymerizable to heat resin polymer by the application to said oil o1'heat alone. said last-mentioned hydrocarbons being present in saidhydrocarbon oil in amount greater than approximately 25% of the totalunsaturation present in said hydrocarbon oil boiling between 210 C. and350 Cj as determined by bromine titration, comprising polymerizing inadmixture both types of said polymerizable hydrocarbons contained insaid hydrocarbon oil to form catalytic resin polymer by treating saidhydrocarbon oil with activated clay. 6. Resin produced by the process ofclaim l. '1. Resin produced by the process of claim 11. 8. Resinproduced by the process of claim 3. 9. Resin produced by the process ofclaim 4. 10. Resin produced by the process of claim 5. 1l. A process forproducing a hydrocarbon resin from a hydrocarbon oil which has beenphysically separated from tar-water emulsion produced in the vapor phasepyrolysis in the presence of steam of a naphthenie petroleum oil andwhich is free from and of greater volatility than the pitch of said tar,said hydrocarbon oil containing in addition to hydrocarbons boilingbetween 210 C. and 350 C. which are not polymerizable by the applicationto said oil of heat alone but which are poiymerizable to catalytic resinpolymer by treating said oil with a resin-producing catalyst, otherhydrocarbons boiling between 210 C. and 350 C. which are polymerizableto catalytic resin polymer. by treating said oil with a resinproducingcatalyst but which last-mentioned hydrocarbons are also polymerizable toheat resin `polymer by the application to said oil of heat alone, saidlast-mentioned hydrocarbons being presentl in said hydrocarbon oil inamount greater than approximately 15% of the total unsaturation presentin said hydrocarbon oil boiling between 210 C. and 350 C. as determinedby bromine titration, comprising polymerizing in admixture both types ofsaid polymerizable hydrocarbons contained in said hydrocarbon ol to formcatalytic resin polymer by treating said hydrocarbon oil with aresin-producing catalyst.

WALD() C. AULT.

